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Is it safe to use Ethanol-Free gasoline with an octane of 91 for the Prius?
Yes but a total and absolute waste of money, if there is a lower octane alternative available at a lower price.

Ethanol free gas can give you up to a 3% increase in mileage so.......
if it costs over 3% more it's a waste of money.

Higher octane in an engine that does not need it gives you absolutely nothing and is always a waste of money.
 

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Totally true, but...guys like to do something nice for their car. A tank of 91 is a nice gesture.

E10 gets a bad rep. 10% ethanol in gas works fine, it is the cheapest and least toxic way to increase octane and oxygenate the gas, but a poor choice for long term storage. Always use a stabilizer in stored gasoline. E15 is OK in cars made for it.
 
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